First-cycle voltage hysteresis in Li-rich 3d cathodes associated with molecular O2 trapped in the bulk


Li-rich cathode materials are potential candidates for next-generation Li-ion batteries. However, they exhibit a large voltage hysteresis on the first charge/discharge cycle, which involves a substantial (up to 1 V) loss of voltage and therefore energy density. For Na cathodes, for example Na0.75[Li0.25Mn0.75]O2, voltage hysteresis can be explained by the formation of molecular O2 trapped in voids within the particles. Here we show that this is also the case for Li1.2Ni0.13Co0.13Mn0.54O2. Resonant inelastic X-ray scattering and 17O magic angle spinning NMR spectroscopy show that molecular O2, rather than O22−, forms within the particles on the oxidation of O2− at 4.6 V versus Li+/Li on charge. These O2 molecules are reduced back to O2− on discharge, but at the lower voltage of 3.75 V, which explains the voltage hysteresis in Li-rich cathodes. 17O magic angle spinning NMR spectroscopy indicates a quantity of bulk O2 consistent with the O-redox charge capacity minus the small quantity of O2 loss from the surface. The implication is that O2, trapped in the bulk and lost from the surface, can explain O-redox.

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Fig. 1: Crystal structure and first-cycle load curve.
Fig. 2: Irreversible loss of honeycomb ordering.
Fig. 3: Spectroscopic characterization of O.
Fig. 4: Structural models for TM disorder and the discharge process.
Fig. 5: Mechanism of first-cycle voltage hysteresis.

Data availability

Supporting research data has been deposited in the Oxford Research Archive and is available under the DOI


  1. 1.

    Croguennec, L. & Palacin, M. R. Recent achievements on inorganic electrode materials for lithium-ion batteries. J. Am. Chem. Soc. 137, 3140–3156 (2015).

    Google Scholar 

  2. 2.

    Croy, J. R., Balasubramanian, M., Gallagher, K. G. & Burrell, A. K. Review of the U.S. Department of Energy’s ‘deep dive’ effort to understand voltage fade in Li- and Mn-rich cathodes. Acc. Chem. Res. 48, 2813–2821 (2015).

    Google Scholar 

  3. 3.

    Hy, S. et al. Performance and design considerations for the lithium excess layered oxide positive electrode materials for lithium ion batteries. Energy Environ. Sci. 9, 1931–1954 (2016).

    Google Scholar 

  4. 4.

    Koga, H. et al. Reversible oxygen participation to the redox processes revealed for Li1.20Mn0.54Co0.13Ni0.13O2. J. Electrochem. Soc. 160, A786–A792 (2013).

    Google Scholar 

  5. 5.

    Oishi, M. et al. Direct observation of reversible oxygen anion redox reaction in Li-rich manganese oxide, Li2MnO3, studied by soft X-ray absorption spectroscopy. J. Mater. Chem. A 4, 9293–9302 (2016).

    Google Scholar 

  6. 6.

    Luo, K. et al. Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen. Nat. Chem. 8, 684–691 (2016).

    Google Scholar 

  7. 7.

    Lu, Z., Beaulieu, L. Y., Donaberger, R. A., Thomas, C. L. & Dahn, J. R. Synthesis, structure, and electrochemical behavior of Li[NixLi1/3–2x/3Mn2/3–x/3]O2. J. Electrochem. Soc. 149, A778 (2002).

    Google Scholar 

  8. 8.

    Johnson, C. S. et al. The significance of the Li2MnO3 component in ‘composite’ xLi2MnO3·(1−x)LiMn0.5Ni0.5O2 electrodes. Electrochem. Commun. 6, 1085–1091 (2004).

    Google Scholar 

  9. 9.

    Seo, D.-H. et al. The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials. Nat. Chem. 8, 692–697 (2016).

    Google Scholar 

  10. 10.

    Saubanère, M., McCalla, E., Tarascon, J.-M. & Doublet, M.-L. The intriguing question of anionic redox in high-energy density cathodes for Li-ion batteries. Energy Environ. Sci. 9, 984–991 (2016).

    Google Scholar 

  11. 11.

    Lu, Z. & Dahn, J. R. Understanding the anomalous capacity of Li/Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 cells using in situ X-ray diffraction and electrochemical studies. J. Electrochem. Soc. 149, A815 (2002).

    Google Scholar 

  12. 12.

    Armstrong et al. Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li[Ni0.2Li0.2Mn0.6]O2. J. Am. Chem. Soc. 128, 8694–8698 (2006).

    Google Scholar 

  13. 13.

    Gent, W. E. et al. Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides. Nat. Commun. 8, 2091 (2017).

    Google Scholar 

  14. 14.

    Hong, J. et al. Metal–oxygen decoordination stabilizes anion redox in Li-rich oxides. Nat. Mater. 18, 256–265 (2019).

    Google Scholar 

  15. 15.

    House, R. A. et al. Superstructure control of first-cycle voltage hysteresis in oxygen-redox cathodes. Nature 577, 502–508 (2020).

    Google Scholar 

  16. 16.

    Xie, Y., Saubanère, M. & Doublet, M.-L. Requirements for reversible extra-capacity in Li-rich layered oxides for Li-ion batteries. Energy Environ. Sci. 10, 266–274 (2017).

    Google Scholar 

  17. 17.

    Yabuuchi, N. et al. Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries. Nat. Commun. 7, 13814 (2016).

    Google Scholar 

  18. 18.

    McCalla, E. et al. Visualization of O–O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries. Science 350, 1516–1521 (2015).

    Google Scholar 

  19. 19.

    Chen, Z., Li, J. & Zeng, X. C. Unraveling oxygen evolution in Li-rich oxides: a unified modeling of the intermediate peroxo/superoxo-like dimers. J. Am. Chem. Soc. 141, 10751–10759 (2019).

    Google Scholar 

  20. 20.

    Sathiya, M. et al. Reversible anionic redox chemistry in high-capacity layered-oxide electrodes. Nat. Mater. 12, 827–835 (2013).

    Google Scholar 

  21. 21.

    Foix, D., Sathiya, M., McCalla, E., Tarascon, J.-M. & Gonbeau, D. X-ray photoemission spectroscopy study of cationic and anionic redox processes in high-capacity Li-ion battery layered-oxide electrodes. J. Phys. Chem. C 120, 862–874 (2016).

    Google Scholar 

  22. 22.

    Bréger, J. et al. High-resolution X-ray diffraction, DIFFaX, NMR and first principles study of disorder in the Li2MnO3–Li[Ni1/2Mn1/2]O2 solid solution. J. Solid State Chem. 178, 2575–2585 (2005).

    Google Scholar 

  23. 23.

    Shunmugasundaram, R., Arumugam, R. S. & Dahn, J. R. A study of stacking faults and superlattice ordering in some Li-rich layered transition metal oxide positive electrode materials. J. Electrochem. Soc. 163, A1394–A1400 (2016).

    Google Scholar 

  24. 24.

    Treacy, M. M. J., Newsam, J. M. & Deem, M. W. A general recursion method for calculating diffracted intensities from crystals containing planar faults. Proc. R. Soc. Lond. A 433, 499–520 (1991).

    MATH  Google Scholar 

  25. 25.

    Luo, K. et al. Anion redox chemistry in the cobalt free 3d transition metal oxide intercalation electrode Li[Li0.2Ni0.2Mn0.6]O2. J. Am. Chem. Soc. 138, 11211–11218 (2016).

    Google Scholar 

  26. 26.

    Assat, G. & Tarascon, J. M. Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries. Nat. Energy 3, 373–386 (2018).

    Google Scholar 

  27. 27.

    Zhu, Z. et al. Gradient Li-rich oxide cathode particles immunized against oxygen release by a molten salt treatment. Nat. Energy 4, 1049–1058 (2019).

    Google Scholar 

  28. 28.

    Qiu, B. et al. Gas–solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries. Nat. Commun. 7, 12108 (2016).

    Google Scholar 

  29. 29.

    Zhao, E. et al. Local structure adaptability through multi cations for oxygen redox accommodation in Li-rich layered oxides. Energy Storage Mater. 24, 384–393 (2020).

    Google Scholar 

  30. 30.

    Kleiner, K. et al. Origin of high capacity and poor cycling stability of Li-rich layered oxides—a long-duration in situ synchrotron powder diffraction study. Chem. Mater. 30, 3656–3667 (2018).

    Google Scholar 

  31. 31.

    Dogan, F. et al. Solid state NMR studies of Li2MnO3 and Li-rich cathode materials: proton insertion, local structure, and voltage fade. J. Electrochem. Soc. 162, A235–A243 (2015).

    Google Scholar 

  32. 32.

    Hua, W. et al. Structural insights into the formation and voltage degradation of lithium- and manganese-rich layered oxides. Nat. Commun. 10, 5365 (2019).

    Google Scholar 

  33. 33.

    Gent, W. E., Abate, I. I., Yang, W., Nazar, L. F. & Chueh, W. C. Design rules for high-valent redox in intercalation electrodes. Joule 4, 1369–1397 (2020).

    Google Scholar 

  34. 34.

    Arhammar, C. et al. Unveiling the complex electronic structure of amorphous metal oxides. Proc. Natl Acad. Sci. USA 108, 6355–6360 (2011).

    Google Scholar 

  35. 35.

    Rubensson, J.-E., Pietzsch, A. & Hennies, F. Vibrationally resolved resonant inelastic soft X-ray scattering spectra of free molecules. J. Electron Spectros. Relat. Phenom. 185, 294–300 (2012).

    Google Scholar 

  36. 36.

    Weber, A. & McGinnis, E. A. The Raman spectrum of gaseous oxygen. J. Mol. Spectrosc. 4, 195–200 (1960).

    Google Scholar 

  37. 37.

    Radjenovic, P. M. & Hardwick, L. J. Evaluating chemical bonding in dioxides for the development of metal–oxygen batteries: vibrational spectroscopic trends of dioxygenyls, dioxygen, superoxides and peroxides. Phys. Chem. Chem. Phys. 21, 1552–1563 (2019).

    Google Scholar 

  38. 38.

    Lebens-Higgins, Z. W. et al. Distinction between intrinsic and X-ray-induced oxidized oxygen states in Li-rich 3d layered oxides and LiAlO2. J. Phys. Chem. C 123, 13201–13207 (2019).

    Google Scholar 

  39. 39.

    Dundon, J. M. 17O NMR in liquid O2. J. Chem. Phys. 76, 2171–2173 (1982).

    Google Scholar 

  40. 40.

    Rana, J. et al. Quantifying the capacity contributions during activation of Li2MnO3. ACS Energy Lett. 5, 634–641 (2020).

    Google Scholar 

  41. 41.

    Li, X. et al. Direct visualization of the reversible O2−/O redox process in Li-rich cathode materials. Adv. Mater. 30, 1705197 (2018).

    Google Scholar 

  42. 42.

    Singer, A. et al. Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging. Nat. Energy 3, 641–647 (2018).

    Google Scholar 

  43. 43.

    Jones, L. et al. Smart Align—a new tool for robust non-rigid registration of scanning microscope data. Adv. Struct. Chem. Imaging 1, 8 (2015).

    Google Scholar 

  44. 44.

    Cococcioni, M. & de Gironcoli, S. Linear response approach to the calculation of the effective interaction parameters in the LDA+U method. Phys. Rev. B 71, 035105 (2005).

    Google Scholar 

  45. 45.

    Giannozzi, P. et al. QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. J. Phys. Condens. Matter 21, 395502 (2009).

    Google Scholar 

  46. 46.

    Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    Google Scholar 

  47. 47.

    Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

    Google Scholar 

  48. 48.

    Heyd, J., Scuseria, G. E. & Ernzerhof, M. Hybrid functionals based on a screened Coulomb potential. J. Chem. Phys. 118, 8207–8215 (2003).

    Google Scholar 

  49. 49.

    Massiot, D. et al. Modelling one- and two-dimensional solid-state NMR spectra. Magn. Reson. Chem. 40, 70–76 (2002).

    Google Scholar 

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P.G.B. is indebted to the EPSRC, including the SUPERGEN programme (EP/L019469/1), the Henry Royce Institute for Advanced Materials (EP/R00661X/1, EP/S019367/1 and EP/R010145/1) and the Faraday Institution (FIRG007 and FIRG008) for financial support. We acknowledge Diamond Light Source for time on I21 under proposal MM23889-1. Support from the EPSRC (EP/K040375/1 ‘South of England Analytical Electron Microscope’) is also acknowledged. We acknowledge the resources provided by the Cambridge Tier-2 system operated by the University of Cambridge Research Computing Service ( funded by EPSRC Tier-2 capital grant EP/P020259/1, via the BATTDesign and AMAiB projects. The UK 850 MHz solid-state NMR Facility used in this research was funded by EPSRC and BBSRC (contract reference PR140003), as well as the University of Warwick, which included via part funding through Birmingham Science City Advanced Materials Projects 1 and 2 supported by Advantage West Midlands (AWM) and the European Regional Development Fund (ERDF).

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R.A.H. conceived and conducted the experimental work with contributions from J.-J.M. and E.B. G.J.R. collected, processed and interpreted the NMR data. M.A.P.-O. performed and interpreted the DFT calculations. A.W.R. performed the ADF-STEM measurements. R.A.H. and J.-J.M. working closely with K.-J. Z. and A.N. and M.G.-F. conducted, processed and interpreted the RIXS and soft XAS measurements. R.A.H. and P.G.B. wrote the manuscript with contributions from all the authors.

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Correspondence to Peter G. Bruce.

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House, R.A., Rees, G.J., Pérez-Osorio, M.A. et al. First-cycle voltage hysteresis in Li-rich 3d cathodes associated with molecular O2 trapped in the bulk. Nat Energy 5, 777–785 (2020).

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